CN105576085B - The method for manufacturing the method for luminescent device and manufacturing group III nitride semiconductor - Google Patents
The method for manufacturing the method for luminescent device and manufacturing group III nitride semiconductor Download PDFInfo
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- CN105576085B CN105576085B CN201510729034.9A CN201510729034A CN105576085B CN 105576085 B CN105576085 B CN 105576085B CN 201510729034 A CN201510729034 A CN 201510729034A CN 105576085 B CN105576085 B CN 105576085B
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 49
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 158
- 239000011241 protective layer Substances 0.000 claims abstract description 133
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract description 19
- 230000004888 barrier function Effects 0.000 claims description 34
- 229910002704 AlGaN Inorganic materials 0.000 claims description 17
- 229910052738 indium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 11
- 229910052594 sapphire Inorganic materials 0.000 description 9
- 239000010980 sapphire Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 Pentadienyl Chemical group 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- UPGUYPUREGXCCQ-UHFFFAOYSA-N cerium(3+) indium(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[In+3].[Ce+3] UPGUYPUREGXCCQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Led Devices (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a kind of method for manufacturing luminescent device and the methods for manufacturing group III nitride semiconductor.In well layer, by MOCVD with to the identical temperature of temperature used in well layer under formed the first InGaN protective layer.TMI is supplied by pulsed.TMI supply amount is kept constant with being greater than 0 μm of ol/min and being not more than the predetermined value of 2 μm of ol/min.In addition, duty ratio is kept constant with the predetermined value greater than 0 and no more than 0.95.The In ratio of components of first protective layer is almost directly proportional to duty ratio.The In ratio of components of the first protective layer can be easily and accurately controlled, by control duty ratio to have In ratio of components in the range of being greater than 0 atom % and being not more than 3 atom %.
Description
Technical field
The present invention relates to the method for manufacturing group iii nitride semiconductor light-emitting device and for manufacturing Section III
The method of group-III nitride semiconductor, more particularly, the present invention relate to form the group III nitride semiconductor comprising In
Method.
Background technique
MQW structure is widely used as the luminescent layer of group iii nitride semiconductor light-emitting device, the sequence in MQW structure
Ground is simultaneously repeatedly deposited with InGaN well layer and AlGaN potential barrier.Because barrier layer is formed by AlGaN, the growth of barrier layer
Temperature must be higher than the growth temperature of well layer, to obtain excellent crystallinity.Therefore, it is necessary to increase temperature after forming well layer
Degree, then grows barrier layer.However, thus leading to luminous efficiency reduction or luminous wave since heating evaporates In from well layer
Long variation.Therefore, it is provided between well layer and barrier layer and is grown at temperature identical with the growth temperature of well layer
Protective layer, to prevent the evaporation of In.
Japanese Laid-Open Patent Publication (special open) the 2010-80619th describe protective layer with AlGaN single layer structure or
The layered structure of person GaN and AlGaN.In addition, Japanese Laid-Open Patent Publication (special open) the 2012-216751st describes protective layer
By with a thickness ofThe GaN of (0.6nm) is formed.In addition, Japanese Laid-Open Patent Publication (special open) the 2001-332763rd describes
Protective layer is formed by the InGaN of the In ratio of components with 7 atom % to 60 atom %.
Because protective layer be grown in at the identical temperature of temperature used in well layer, the crystallinity of protective layer
It is low, cause luminous efficiency to reduce.Therefore, inventor in protective layer in research by combining a small amount of In living as surface
Property agent (making the impurity of surface planarisation) Lai Tigao crystal quality.The amount of In is less, the reason is that having in conjunction with excessive In opposite
Effect and lead to the deterioration of crystal quality.
However, because protective layer with to the identical temperature of temperature used in well layer under grow, protective layer is low
It is grown under temperature.In is easily incorporated into crystal at low temperature, and even if supplies the unstripped gas as the source In of minimum
Body still includes a certain amount of In in crystal.Therefore, protective layer cannot be nitrogenized by the III-th family with low In ratio of components
Object semiconductor is formed.
Summary of the invention
In view of the foregoing, the object of the present invention is to can be formed at a low growth temperature by with low In group
At than group III nitride semiconductor made of protective layer.
In one aspect of the invention, it provides a kind of for manufacturing group iii nitride semiconductor light-emitting device
Method, the group iii nitride semiconductor light-emitting device include the luminescent layer with MQW structure, this method comprises:
Form luminescent layer by sequentially and repeatedly depositing following layers using MOCVD: well layer, well layer is by including In's
Group III nitride semiconductor is made；First protective layer, the first protective layer is by the group III nitride semiconductor system comprising In
At the band gap of the first protective layer is equal to or more than the band gap of well layer；And barrier layer, barrier layer are partly led by III-th family nitride
System is at the band gap of barrier layer is greater than the band gap of well layer；Wherein
With at the identical temperature of temperature used in well layer, by pulsed supply as the source In unstrpped gas come
The first protective layer is formed, to obtain the In ratio of components for being greater than 0 atom % and being not more than 3 atom %.Ratio of components atom % means half
The atomic percent of conductor crystal.
It is to repeat the supply of gas and not supplying for gas that pulsed, which is supplied as the unstrpped gas in the source In,.
When pulsed supplies unstrpped gas as the source In, pulse width, pulse cycle, pulse height (as
The supply amount of the unstrpped gas in the source In) it can be controlled so as to arbitrary value, as long as the number of pulse is no less than each first protective layer
Two pulses.It can be by controlling duty ratio (the ratio between pulse width and pulse cycle) specifically come easily and accurate
Ground controls In ratio of components.This is because In ratio of components is almost directly proportional to duty ratio.Duty ratio can be greater than 0 and be not more than
0.95.In order to be easier to control, preferably by duty ratio control in the range of 0.35 to 0.95, and more preferably 0.35
To in the range of 0.75.
The In ratio of components of first protective layer is preferably 1 atom % to 3 atom %, and more preferably 1 atom % is extremely
2.5 atom %, to improve the crystal quality and luminous efficiency of the first protective layer.
The supply amount of unstrpped gas as the source In is preferably more than 0 μm of ol/min and no more than 2 μm of ol/min.As a result,
First protective layer has greater than 0 atom % and is not more than the In ratio of components of 3 atom %.
Well layer and the growth temperature of the first protective layer are preferably 700 DEG C to 850 DEG C.Well layer In with higher as a result,
Ratio of components, and emission wavelength easily and is accurately controlled.Well layer and the growth temperature of the first protective layer need not complete phases
Together, and about ± 10 DEG C of tolerance is allowed.
It can be formed between the first protective layer and barrier layer made of the group III nitride semiconductor comprising Al
The Al ratio of components of two protective layers and the second protective layer can make the band gap of the second protective layer greater than the band of the first protective layer
Gap.Thus, it is possible to improve the Lattice Matching between the first protective layer and barrier layer, cause the raising of luminous efficiency.
First protective layer can be formed by InGaN or AlGaInN.In addition, the second protective layer can by AlGaN or
AlGaInN is formed.
Unstrpped gas as the source In can be the organic metal gas comprising In, for example, trimethyl indium (TMI；In
(GH3)3) or triethylindium (TEI；In(C2H5)3)。
In another aspect of the invention, a kind of method for manufacturing group III nitride semiconductor is provided,
In, by MOCVD 700 DEG C to 850 DEG C at a temperature of formed include In group III nitride semiconductor in the case where,
The unstrpped gas as the source In is supplied by pulsed to obtain greater than 0 atom % and be not more than the In ratio of components of 3 atom %.
Method according to the present invention for manufacturing group III nitride semiconductor, though with to used in well layer
In the case where forming the protective layer made of the group III nitride semiconductor comprising In at the identical temperature of temperature, that is,
It says, in the case where forming the group III nitride semiconductor comprising In at low temperature, can also be supplied by pulsed and be used as In
The unstrpped gas in source reduces In ratio of components.More specifically, In ratio of components can reduce to more than 0 atom % and former no more than 3
Sub- %.
Detailed description of the invention
Since in the case where being considered in conjunction with the accompanying, referring to the described in detail below of preferred embodiment, of the invention is each
Kind of other purposes, feature and many attendant advantages will become better understood, it is possible to be readily appreciated that of the invention various
Other purposes, feature and many attendant advantages, in which:
Fig. 1 shows the structure of the luminescent device according to embodiment 1；
Fig. 2 shows the structures of luminescent layer 13；
Fig. 3 A to Fig. 3 D is to show the schematic diagram of the technique for manufacturing the luminescent device according to embodiment 1；
Fig. 4 A to Fig. 4 E is to show the schematic diagram for the technique for being used to form luminescent layer 13；
Fig. 5 is to show the figure of TMI supply amount and the relationship between the time；
Fig. 6 is to show the figure of the relationship between duty ratio and the In ratio of components of the first protective layer 13B；And
Fig. 7 is to show the figure of the relationship between the In ratio of components and relative intensity of the first protective layer 13B.
Specific embodiment
Specific embodiments of the present invention are described referring next to attached drawing.However, the present invention is not limited to the embodiment party
Case.
Embodiment 1
Fig. 1 shows the structure of the group III nitride semiconductor according to embodiment 1.As shown in Figure 1, according to implementation
The luminescent device of scheme 1 includes: Sapphire Substrate 10；N-contact layer 11 in Sapphire Substrate 10 is set；It is arranged in N-shaped
N-shaped coating 12 on contact layer 11；Luminescent layer 13 on N-shaped coating 12 is set；P-type coating on luminescent layer 13 is set
14；And the P type contact layer 15 on p-type coating 14 is set.In addition, including: that setting exists according to the luminescent device of embodiment 1
Transparent electrode 16 in a part of P type contact layer 15；P-electrode 17 in transparent electrode 16 is set；And setting connects in N-shaped
N-electrode 18 in a part of contact layer 11 exposed by groove 19.It is with above-mentioned according to the luminescent device of embodiment 1
The face up type of structure.
Sapphire Substrate 10 is the growth substrates for growing group III nitride semiconductor crystal in its main surface.
The main surface is such as face a or the face c.The surface of Sapphire Substrate 10 can coarse chemical conversion point or candy strip, mentioned with improving light
Take efficiency.Other than Sapphire Substrate, the substrate made of the material of such as GaN, SiC, ZnO and Si can be used.
AlN buffer layer (not shown) is provided with n-contact layer 11 on the surface of the out-of-flatness of Sapphire Substrate 10.
Other than AlN, buffer layer can be formed by GaN or AlGaN.In n-contact layer 11, it is provided with N-shaped coating 12.N-shaped connects
Contact layer 11 is such as 1 × 10 by Si concentration18/cm3Or bigger n-GaN is formed.N-contact layer 11 may include having different Si
Multiple layers of concentration.N-shaped coating 12 has the superlattices knot for for example wherein alternately and being repeatedly deposited with InGaN and n-GaN
Structure.The ESD layer for improving electrostatic breakdown voltage can be formed between n-contact layer 11 and N-shaped coating 12.ESD layer is for example
For in the layer for being wherein deposited with undoped GaN and n-GaN.
As shown in Fig. 2, luminescent layer 13 has the MQW structure for being wherein repeatedly deposited with multiple layer units, each layer unit
Including well layer 13A, the first protective layer 13B, the second protective layer 13C and the barrier layer 13D deposited in order.Duplicate number is three
It is secondary to ten times.Both N-shaped coating 12 and p-type coating 14 are all contacted with barrier layer 13D.The overall thickness of luminescent layer 13 be 500nm extremely
700nm.Will then be described the detailed construction of luminescent layer 13.
On luminescent layer 13, it is sequentially deposited p-type coating 14 and P type contact layer 15.P-type coating 14 can have wherein
Alternately and repeatedly it is deposited with the superlattice structure of p-InGaN and p-AlGaN.The In ratio of components of p-InGaN be 5 atom % extremely
12 atom %, and with a thickness of 2nm.In addition, the Al ratio of components of p-AlGaN is 25 atom % to 40 atom %, and with a thickness of
2.5nm.P type contact layer 15 is 1 × 10 by Mg concentration19/cm3Or bigger p-GaN is formed, and with a thickness of 80nm.P-type contact
Layer 15 may include multiple layers with different Mg concentration.
Transparent electrode 16 is formed by ITO, with the whole surface of almost blanket p-type contact layer 15.In addition to ito, transparent
Electrode 16 can be formed by such as IZO (indium-zinc oxide) or ICO (indium cerium oxide).
P-electrode 17 is provided in transparent electrode 16.It is arranged in the n-contact layer 11 exposed in the bottom surface of groove 19
There is n-electrode 18.Groove 19 is arranged in a part of semiconductor layer, and has from the surface of P type contact layer 15 and extend to N-shaped
The depth of contact layer 11.P-electrode 17 and n-electrode 18 have wiring welding disk connected to it and with welding disk it is consecutive,
The wire connecting portion extended with linearity pattern.
[specific structure of luminescent layer 13]
The detailed construction of luminescent layer 13 is described next with reference to Fig. 2.
Well layer 13A is formed by InGaN of with In ratio of components, emission wavelength in the range of 380nm to 460nm.Trap
The thickness of layer 13A is in the range of 1nm to 5nm.
First protective layer 13B is configured to contact with well layer 13A and on well layer 13A.First protective layer 13B is following
Layer, this layer is provided in be formed after well layer 13A prevents In from trap during the temperature for being heated to being used to form barrier layer 13D
Layer 13A evaporation.
First protective layer 13B is formed by InGaN, and the band gap of the first protective layer 13B is smaller than the band gap of well layer 13A.In Section III
In the case that group-III nitride semiconductor is doped with In, In is used as surfactant, to inhibit on longitudinal direction (thickness direction)
It grows and promotes the growth on lateral (direction for being parallel to main surface).Therefore, by will act as surfactant
In is integrated in the first protective layer 13B, and the crystal quality of the first protective layer is improved, and which thereby enhances luminous efficiency.However,
In the case where In ratio of components is greater than 3 atom %, new crystal defect occurs, and crystal quality deteriorates, and causes device reliable
Property reduce, this is undesirable.Therefore, In ratio of components is greater than 0 atom % and is not more than 3 atom %.It is highly preferred that In ratio of components
For 0.5 atom % to 3 atom %, and it is further preferred that In ratio of components is 1 atom % to 2.5 atom %.First protective layer
13B can be formed by the group III nitride semiconductor (for example, AlGaInN) comprising In.In addition, because the first protective layer 13B
Crystal in In ratio it is small, so crystal can be the GaN doped with In, rather than mixed crystal or In compound semiconductor.So
And in the present specification, it is written as InGaN, and be described as mixed crystal.
Because the first protective layer 13B with to the identical temperature of temperature used in well layer 13A under grow,
InGaN generally can not be formed to have greater than 0 atom % and be not more than the In ratio of components of 3 atom %.Therefore, according to subsequent institute
The forming method stated forms the InGaN with low In ratio of components.
First protective layer 13B with a thickness of 0.2nm to 1.8nm.As used herein, " the thickness of the first protective layer 13B
Thickness of the degree " not instead of when the first protective layer 13B formation, even if after forming the heating after the first protective layer 13B
Also retain the thickness without the first protective layer 13B being thermal decomposited.Such thickness range reduces in the first protective layer 13B
Carrier capture or compound, which thereby enhance luminous efficiency.Thickness more preferably in the range of 0.5nm to 1.0nm, and
And it is further preferred that in the range of 2 molecular layers to 3 molecular layers.The thickness of one monolayer and the c-axis of GaN are brilliant
The 1/2 of lattice constant is corresponding, and two monolayers with a thickness of 0.5185nm.By the way that the lattice having with well layer 13A is arranged
Second protective layer 13C of the close lattice constant of constant, improves the production layer between the second protective layer 13C and well layer 13A
Overall crystallinity, which thereby enhance luminous efficiency.
First protective layer 13B is not limited to InGaN, but can be for the group III nitride semiconductor comprising In for example
AlGaInN。
Second protective layer 13C is configured to contact with the first protective layer 13B and on the first protective layer 13B.Setting second
Protective layer 13C which thereby enhances barrier layer 13D to reduce the difference of the lattice constant between the first protective layer 13B and barrier layer 13D
Crystallinity.
Second protective layer 13C is formed by AlGaN.Second protective layer 13C can have arbitrary Al ratio of components, as long as second
The band gap of protective layer 13C is bigger than the band gap of the first protective layer 13B.However, the band gap and barrier layer of the second protective layer 13C
The difference of the band gap of 13D is preferably smaller.Al ratio of components is preferably in the range of 1.5 atom % to 3.5 atom %, and into one
It walks preferably, in the range of 2 atom % to 3 atom %.Second protective layer 13C can be the III-th family nitride comprising Al
Semiconductor such as AlGaInN.In this case, In ratio of components can be identical as the In ratio of components of the first protective layer 13B, and
The crystallinity expection of second protective layer 13C is improved.
Second protective layer 13C with a thickness of 0.2nm to 1.8nm.Such thickness range reduces in the second protective layer 13C
In carrier capture or compound, which thereby enhance luminous efficiency.Thickness is more preferably the range in 0.5nm to 1.6nm
It is interior, and it is further preferred that in the range of 0.5nm to 1.1nm.
Barrier layer 13D is formed by AlGaN.Al ratio of components is 3 atom % to 10 atom %, and with a thickness of 1nm to 10nm.
Barrier layer 13D is not limited to single AlGaN layer, but may include multiple layers, such as multiple layers with different Al ratio of components.Gesture
Barrier layer 13D can be such as AlGaInN of the group III nitride semiconductor comprising Al, as long as the band gap of barrier layer 13D compares well layer
The band gap of 13A is big.
In embodiment 1, the layered structure of the first protective layer 13B and the second protective layer 13C are arranged in well layer 13A
With the protective layer between barrier layer 13D.However, it is possible to only form the first protection in the case where not forming the second protective layer 13C
Layer 13B.In this case, the first protective layer 13B is preferably formed by AlGaInN, with compared with well layer 13A in terms of band gap
With bigger difference.
[for manufacturing the technique of luminescent device]
It is described next with reference to Fig. 3 A to Fig. 3 D and Fig. 4 A to Fig. 4 E for manufacturing shining according to embodiment 1
The process of device.By Atmospheric pressure MOCVD come crystal growth group III nitride semiconductor.Unstrpped gas used in MOCVD
It is as described below: ammonia (NH3) it is used as nitrogen source；Trimethyl gallium (TMG；Ga(GH3)3) it is used as the source Ga；Trimethyl indium (TMI；In
(GH3)3) it is used as the source In；Trimethyl aluminium (TMA；Al(GH3)3) it is used as the source Al；Silane (SiH4) it is used as n-type doping gas；Bis- (rings
Pentadienyl) magnesium (CP2MG；Mg(C5H5)2) it is used as p-type doping gas；And H2And N2As carrier gas.Needless to say, in addition to above-mentioned
Except material, it can be used and made by conventional MOCVD material used in the crystal growth of group III nitride semiconductor
For unstrpped gas.For example, triethylindium (TEI can be used other than TMI；In(C2H5)3) it is used as the source In.
Firstly, preparing Sapphire Substrate 10, and heating Sapphire Substrate 10 is used for surface cleaning in a hydrogen atmosphere.
Next, by MOCVD 400 DEG C at a temperature of in Sapphire Substrate 10 formed AlN buffer layer (not shown).
Other than AlN, GaN and AlGaN can be used.Then, by MOCVD under 1100 DEG C of growth temperature shape on the buffer layer
At n-contact layer 11.Then, in n-contact layer 11, N-shaped coating 12 is formed under 830 DEG C of growth temperature by MOCVD
(Fig. 3 A).
Then, on N-shaped coating 12, the luminescent layer 13 with MQW structure is formed by MOCVD.By repeatedly depositing
Three layer units form luminescent layer 13 to ten layer units, and each layer unit includes the well layer 13A deposited in order, the first guarantor
Sheath 13B, the second protective layer 13C and barrier layer 13D (Fig. 3 B).
Here, by the technique to form luminescent layer 13 is described more fully with reference to Fig. 4 A to Fig. 4 E and Fig. 5.
Firstly, on N-shaped coating 12, by MOCVD 765 DEG C to 985 DEG C at a temperature of form AlGaN potential barrier 13D
(Fig. 4 A).
Then, temperature is reduced to temperature lower than the growth temperature of barrier layer 13D, in the range of 700 DEG C to 850 DEG C
Degree, and InGaN well layer 13A (Fig. 4 B) is then formed by MOCVD.Importantly, improving growth temperature to improve well layer
The crystal quality of 13A and barrier layer 13D, while keeping desired wavelength.Therefore, the growth temperature of well layer 13A is preferably 750
It DEG C to 850 DEG C, and is further preferably 800 DEG C to 850 DEG C.
Next, on well layer 13A, by MOCVD with to the identical temperature of temperature used in well layer 13A under by
InGaN forms the first protective layer 13B (Fig. 4 C).However, permitting for the growth temperature of well layer 13A and the first protective layer 13B
Perhaps about ± 10 DEG C of tolerance.
Here, continuously feed the ammonia as nitrogen source when forming the first protective layer 13B, as the source Ga TMG and
Carrier gas, and be that (Fig. 5) is supplied by the pulsed for repeating to supply and do not supply to carry out as the TMI in the source In.This passes through
It is carried out with scheduled circulation to open and close the valve of TMI supply pipe.The number of pulse can be arbitrary value, as long as pulse
Number be no less than two.The supply amount of TMI be greater than 0 μm of ol/min and be not more than 2 μm of ol/min in the range of
Predetermined amount is kept constant.In addition, duty ratio D is kept constant with the predetermined value greater than 0 and no more than 0.95.Duty ratio D is pulse
The ratio between width t and pulse cycle T, (the TMI service time that t is each cycle T), and D=t/T.
It, can by control duty ratio D because the In ratio of components and duty ratio D of the first protective layer 13B are almost directly proportional
Easily and accurately to control In ratio of components.It has almost been determined by TMI supply amount, TMG supply amount and growth time at this
Proportionality coefficient in the case of kind.
Then, the first protective layer 13B is formed by control duty ratio D, so that the first protective layer 13B, which has, is being greater than 0
Atom % and the In ratio of components being not more than in the range of 3 atom %.Such In ratio of components of first protective layer 13B can be improved
The crystal quality of first protective layer 13B thereby reduces the carrier loss in the first protective layer 13B.Therefore, it can be improved
The luminous efficiency of luminescent device.In addition, by controlling In ratio of components at no more than 3 atom %, it is therefore prevented that be integrated to crystalline substance by In
New defect caused by body, and inhibit the reduction of device reliability.
The thickness of the first protective layer 13B can be controlled by the number of pulse, so that the first protective layer 13B is formed as having
There is the thickness of 0.2nm to 1.8nm.
As mentioned above, the first protective layer 13B of InGaN can supply TMI by pulsed and control duty ratio D
And it is formed to have greater than 0 atom % and is not more than the In ratio of components of 3 atom %, which thereby enhance luminous efficiency.In order into one
Step improves luminous efficiency, and the In ratio of components of the first protective layer 13B is preferably 1 atom % to 3 atom %, and further preferably
Ground is 1 atom % to 2.5 atom %.
When being actually formed the first protective layer 13B, it is difficult to by the control of the In concentration of the first protective layer 13B at no more than 1 ×
1016/cm3.Therefore, substantially mean acquisition 1 × 10 " greater than the In ratio of components of 0 atom % "16/cm3Or bigger In concentration
In ratio of components.
In addition it is possible to use the TMI of any supply amount (pulse height), if the supply amount of TMI be greater than 0 μm of ol/min and
No more than 2 μm ol/min.However, it is preferable that value as small as possible, that is, in MOCVD system it is possible in structure
The smallest value.The supply amount of TMI is preferably controlled, so that the speed of growth of the speed of growth than well layer 13A of the first protective layer 13B
Slowly.This is the crystallinity in order to improve the first protective layer 13B.
Pulse width t and cycle period T can be arbitrary value, as long as duty ratio D is within the above range.
In addition, the various conditions of the pulsed supply of TMI are (for example, pulse is high in the growth period of the first protective layer 13B
Degree or duty ratio D) it can keep constant or change.
Then, on the first protective layer 13B, by MOCVD identical with to temperature used in the first protective layer 13B
At a temperature of the second protective layer 13C (Fig. 4 D) is formed by AlGaN.
Next, stopping the supply of unstrpped gas, and temperature is made to increase to higher than the growth temperature of the second protective layer 13C
, temperature within the scope of 765 DEG C to 985 DEG C.Although subtracting the second protective layer 13C gradually
It is thin, but the second protective layer 13C can retain until barrier layer 13D growth starts, the reason is that the thickness of the second protective layer 13C
Degree setting is within the above range.In addition, the presence of the second protective layer 13C prevents In to evaporate from well layer 13A, and inhibit pair
The damage of well layer 13A, which thereby enhances luminous efficiency.
Then, restart the supply of unstrpped gas, and on the second protective layer 13C, protected by MOCVD than second
The growth temperature of sheath 13C is high, by AlGaN forms barrier layer 13D (Fig. 4 E) at a temperature in the range of 765 DEG C to 985 DEG C.
By being grown at a temperature of higher than the temperature of the first protective layer 13B and the second protective layer 13C, barrier layer 13D can be given birth to
Grow up to excellent crystallinity, which thereby enhances luminous efficiency.Well layer 13A, the first protective layer 13B and the second protective layer 13C
Growth temperature and the difference of growth temperature of barrier layer 13D be preferably 50 DEG C to 200 DEG C.The case where temperature difference is less than 50 DEG C
Under, the crystallinity of barrier layer 13D will not be improved sufficiently, and in the case where temperature difference is more than 200 DEG C, the crystallization of well layer 13A
Degree deterioration.
Hereafter, on barrier layer 13D, in method identical with methods mentioned above by well layer 13A, the first protective layer
13B, the second protective layer 13C and barrier layer 13D sequentially and are repeatedly deposited several times, are consequently formed with shown in Fig. 2
The luminescent layer 13 of MQW structure.
Next, being sequentially formed p-type coating 14 and P type contact layer 15 on luminescent layer 13 by MOCVD, and pass through
Sputtering is vapor-deposited in a part (not forming the part of groove 19 during in next step on it) of P type contact layer 15
It is formed transparent electrode 16 (Fig. 3 C).
Then, dry etching is carried out come shape by the surface of the transparent electrode 16 not formed on it to P type contact layer 15
At the groove (Fig. 3 D) with the depth for touching n-contact layer 11.After forming groove 19, transparent electrode 16 can be formed.
Next, forming p-electrode 17 on the predetermined portions of transparent electrode 16 by vapor deposition, and contacted in N-shaped
N-electrode 18 is formed on the predetermined portions of layer 11 exposed in the bottom of groove 19.P-electrode 17 and n-electrode can be initially formed
Any one of 18.When p-electrode 17 and n-electrode 18 are formed from the same material, p-electrode 17 or n-electrode can be formed simultaneously
18.Hereafter, activate magnesium by carrying out annealing in a nitrogen atmosphere, and p-type coating 14 and P type contact layer 15 realize p-type
Conduction.The annealing conducted for realizing p-type can be carried out before forming p-electrode 17 and n-electrode 18.In addition, in transparent electrode
16 formed by such as ITO and annealed with for its crystallization when, to the annealing of transparent electrode 16 can with realize p-type pass
The annealing led is identical.Therefore, the luminescent device shown in FIG. 1 according to embodiment 1 has been manufactured.
By the method for manufacturing the luminescent device according to embodiment 1, though with to temperature used in well layer 13A
Spend it is identical in a low temperature of when forming the first protective layer 13B by InGaN, In ratio of components can also be greater than 0 atom % and former no more than 3
Sub- %, the reason is that the unstrpped gas as the source In is pulsed supply.Therefore, it can be improved the crystal matter of the first protective layer 13B
Amount, reduces the carrier loss in the first protective layer 13B.Therefore, it can be improved the luminous efficiency of luminescent device.
[experimental result]
It is described below the result for the various experiments carried out according to the luminescent device of embodiment 1.
In the case where pulsed supplies TMI when forming the first protective layer 13B, In group is measured at different duty D
At than.Use following four duty ratio D:0,0.25,0.5 and 1.Constant TMI supply amount is 2 μm of ol/min, pulse cycle T
It is 12 seconds, and the number of pulse is 2.In addition, the growth temperature of the first protective layer 13B is 820 DEG C.Duty ratio D=0 means not
The case where supplying TMI, and duty ratio D=1 means the case where continuously feeding TMI.
Fig. 6 is to show the figure of the relationship between duty ratio D and the In ratio of components of the first protective layer 13B.As shown in fig. 6,
As duty ratio D increases from 0, In ratio of components also increases.When duty ratio D reaches 1, In ratio of components is about 3.2 atom %.In group
At almost more directly proportional than to duty ratio D.Thus, it is found that can easily and accurately control the first guarantor by controlling duty ratio D
The In ratio of components of sheath 13B.According to Fig. 6 it has also been found that, when by duty ratio D control at be not more than 0.95 when, can be by In ratio of components
It controls into no more than 3 atom %.More specifically, In ratio of components can be controlled by being 0.35 to 0.95 by duty ratio D control
For 1 atom % to 3 atom %, and by being 0.35 to 0.75 by duty ratio D control, In ratio of components can be controlled former for 1
Sub- % to 2.5 atom %.
Fig. 7 is to show the figure of the relationship between the In ratio of components and relative intensity of the first protective layer 13B.In the first protection
Layer 13B In ratio of components be 0 atom % (namely the first protective layer 13B is formed by AlGaN) in the case where by light output come
Normalizing relative intensity is 1.
As shown in fig. 7, luminous intensity increases with the increase of In component.However, luminous intensity is about 1.7 originals in In ratio of components
Reach peak value at sub- % and then starts to reduce.Luminous intensity is increased up the reason of In ratio of components reaches 1.7 atom % and is recognized
Crystal quality to be the first protective layer 13B is improved, and thereby reduces the carrier loss in the first protective layer 13B.
The reason of luminous intensity reduces in the case where In ratio of components is more than 1.7 atom % is considered as occurring new crystal due to In and lacking
It falls into.It can be clearly seen from Fig. 7, even if luminous intensity is still divided into 0 original than In group in the case where In ratio of components is more than 3 atom %
Luminous intensity at sub- % is big.However, increasing new defect due to the increase of In, device reliability being caused to reduce.Therefore, In
Ratio of components is preferably to be not more than 3 atom %.
Change programme
In embodiment 1, the unstrpped gas cause as the source In is supplied with greater than 0 atom % and not by pulsed
The InGaN of In ratio of components greater than 3 atom % forms the first protective layer 13B of luminescent layer 13.The invention is not limited thereto, as long as packet
Group III nitride semiconductor (for example, InGaN, AlGaInN and AlInN) containing In is formed at low temperature, so that it may which application is originally
Invention.For example, present invention could apply to the layers other than the luminescent layer of luminescent device, and can also be applied in addition to hair
Semiconductor devices except optical device.
In is integrated to the easy degree in crystal and extremely depends sensitively on growth temperature.When growth temperature is high, In
It is difficult to combine.When growth temperature is low, In is easy to combine.
Further, since the structural factor of MOCVD system, TMI supply amount usually at most can be reduced only to certain value.Cause
This, in the case where continuously feeding TMI, the In ratio of components of the group III nitride semiconductor comprising In at most can only subtract
As low as certain minimum value.
In is easily incorporated into crystal at a low growth temperature.Growth temperature is lower, and the minimum value of In ratio of components is higher.
For example, as shown in Figure 6 and Figure 7, when growth temperature is 820 DEG C, In ratio of components can at most be only decreased to 3.2 atom %.So
And the invention enables the values that In ratio of components can be reduced by more than limit value.More specifically, In ratio of components can reduce to more than
0 atom % and be not more than 3 atom %.
Growth of the present invention for the group III nitride semiconductor (more specifically, InGaN and AlGaInN) comprising In
The case where temperature is 700 DEG C to 850 DEG C is effective.By continuously feeding In next life long crystal at this low temperature
In the case of, In ratio of components generally can not be decreased to be greater than 0 atom % and no more than 3 atom %.However, it is possible to by applying this hair
It is bright to form the group III nitride semiconductor with such In ratio of components.
The luminescent device manufactured according to the present invention may be used as the light source of display equipment or the light source of lighting apparatus.
Claims (9)
1. a kind of method for manufacturing group iii nitride semiconductor light-emitting device, the group III nitride semiconductor hair
Optical device includes the luminescent layer with MQW structure, which comprises
Form the luminescent layer: well layer by sequentially and repeatedly depositing following layers using MOCVD, the well layer by comprising
The group III nitride semiconductor of In is made；First protective layer, first protective layer is by the III-th family nitride comprising In
Semiconductor is made, and the band gap of first protective layer is equal to or more than the band gap of the well layer；And barrier layer, the barrier layer
It is made of group III nitride semiconductor, the band gap of the barrier layer is greater than the band gap of the well layer；Wherein
With at the identical temperature of temperature used in the well layer, by pulsed supply as the source In unstrpped gas come
First protective layer is formed, to obtain the In ratio of components for being greater than 0 atom % and being not more than 3 atom %, and wherein
It is formed the made of the group III nitride semiconductor comprising Al between first protective layer and the barrier layer
The Al ratio of components of two protective layers and second protective layer makes the band gap of second protective layer be greater than first protection
The band gap of layer.
2. the method according to claim 1 for manufacturing group iii nitride semiconductor light-emitting device, wherein in pulse
When formula supplies the unstrpped gas as the source In, the In ratio of components of first protective layer is controlled by duty ratio.
3. the method according to claim 2 for manufacturing group iii nitride semiconductor light-emitting device, wherein in pulse
When formula supplies the unstrpped gas as the source In, the duty ratio is greater than 0 and is not more than 0.95.
4. the method according to claim 3 for manufacturing group iii nitride semiconductor light-emitting device, wherein being used as In
The supply amount of the unstrpped gas in source is greater than 0 μm of ol/min and is not more than 2 μm of ol/min.
5. according to any one of claims 1 to 4 for manufacturing the side of group iii nitride semiconductor light-emitting device
Method, wherein the well layer and the growth temperature of first protective layer are 700 DEG C to 850 DEG C.
6. the method according to claim 1 for manufacturing group iii nitride semiconductor light-emitting device, wherein described
One protective layer is formed by InGaN.
7. the method according to claim 5 for manufacturing group iii nitride semiconductor light-emitting device, wherein described
One protective layer is formed by InGaN.
8. the method according to claim 1 for manufacturing group iii nitride semiconductor light-emitting device, wherein described
Two protective layers are formed by AlGaN.
9. according to claim 1 to described in any one of 4 and claim 6 for manufacturing group III nitride semiconductor
The method of luminescent device, wherein the unstrpped gas as the source In is trimethyl indium.
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| CN203192830U (en) * | 2013-03-13 | 2013-09-11 | 扬州中科半导体照明有限公司 | MQW structure of high-brightness GaN-based green LED |
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